Soluble and stable heptazethrenebis(dicarboximide) with a singlet open-shell ground state

A soluble and stable heptazethrene derivative was synthesized and characterized for the first time. This molecule exhibits a singlet biradical character in the ground state, which is the first case among zethrene homologue series. Exceptional stability of this heptazethrenebis(dicarboximide) raises the likelihood of its practical applications in materials science.     

On relativistic effects in ground state potential curves of Zn2, Cd2, and Hg2 dimers. A CCSD(T) study

The ground state potential curves of the Zn2, Cd2, and Hg2 dimers calculated at different levels of theory are presented and compared with each other as well as with experimental and other theoretical studies. The calculations at the level of Dirac-Coulomb Hamiltonian (DCH), 4-component spin-free Hamiltonian, nonrelativistic Lévy-Leblond Hamiltonian and at the level of simple Coulombic correction to DCH are presented. The potential curves are calculated in an all-electron supermolecular approach including the correction to basis set superposition error (BSSE). Electron correlation is treated at the coupled cluster level including single and double excitations and noniterative triple corrections, CCSD(T). In addition, simulations of the temperature dependence of dynamic viscosities in the low-density limit using the obtained ground state potential curves are presented.     

Prediction of vibrational frequencies of UO2(2+) at the CCSD(T) level

Electronic structure calculations at the coupled cluster (CCSD(T)) and density functional theory levels with relativistic effective core potentials and large basis sets were used to predict the isolated uranyl ion frequencies. The effects of anharmonicity and spin-orbit corrections on the harmonic frequencies were calculated. The anharmonic effects are larger than the spin-orbit corrections, but both are small. The anharmonic effects decreased all the frequencies, whereas the spin-orbit corrections increased the stretches and decreased the bend. Overall, these two corrections decreased the harmonic asymmetric stretch frequency by 6 cm-1, the symmetric stretch by 3 cm-1, and the bend by 3 cm-1. The best calculated values for UO22+ for the asymmetric stretch, symmetric stretch, and bend were 1113, 1032, and 174 cm-1, respectively. The separation between the asymmetric and the symmetric stretch band origins was predicted to be 81 cm-1, which is consistent with experimental trends for substituted uranyls in solution and in the solid state. The anharmonic vibrational frequencies of the isoelectronic ThO2 molecule also were calculated and compared to experiment to calibrate the UO22+ results.     

基于图形处理单元与密度拟合近似的单精度耦合簇CCSD和CCSD(T)程序

作者此前工作表明, 在耦合簇CCSD (Coupled-Cluster approaches within the singles and doubles approximation)与CCSD(T) (CCSD approaches augmented by a perturbative treatment of triple excitations)计算中结合单精度数与消费型图形处理单元(GPU), 可以显著提高计算速度. 然而由于CCSD(T)计算对内存的巨大需求以及消费型GPU的内存限制, 在利用消费型GPU进行加速时, 不考虑利用空间对称性的情况下, 此前开发的CCSD(T)程序仅能用于计算300~400个基函数的体系. 利用密度拟合(Density-Fitting, DF)处理双电子积分可以显著降低CCSD(T)计算过程中的内存需求, 本工作发展了基于密度拟合近似并结合单精度数进行运算的DF-CCSD(T)程序, 该程序可用于包含700个基函数的无对称性体系的单点能计算, 以及包含1700个基函数的有对称性体系. 本工作所使用的计算节点配置了型号为Intel I9-10900k的CPU和型号为RTX3090的GPU, 与用双精度数在CPU上的计算相比, 利用单精度数结合GPU进行运算可以将CCSD的计算速度提升16倍, (T)部分可提升40倍左右, 而使用单精度数引入的误差可忽略不计. 在程序开发过程中, 作者发展了一套可利用GPU或CPU结合单精度数或双精度数进行含空间对称性的矩阵操作代码库. 基于该套代码库, 可以显著降低开发含空间对称性的耦合簇代码的难度.     

Improving upon CCSD(T): LambdaCCSD(T). II. Stationary formulation and derivatives

Analytical derivatives are formulated and implemented for the LambdaCCSD(T) method. As the historically first size-extensive and orbitally invariant extension of coupled-cluster (CC) theory to exploit the left-hand ground state eigenvector, it offers a vastly better treatment of bond breaking than does CCSD(T), and points the way toward further generalizations of single-reference CC theory that enhance its accuracy away from equilibrium geometries. Application to diatomic force curves and transition states of several well-characterized reactions are made. Surprisingly, despite LambdaCCSD(T) describing bond breaking much better than CCSD(T), for transition states both methods are extremely close in both structures and activation barriers. Force curves, however, demonstrate the overall superiority of LambdaCCSD(T).     

CCSD(T) study of dimethyl-ether infrared and Raman spectra

CCSD(T) state-of-the-art ab initio calculations are used to determine a vibrationally corrected three-dimensional potential energy surface of dimethyl-ether depending on the two methyl torsions and the COC bending angle. The surface is employed to obtain variationally the lowest vibrational energies that can be populated at very low temperatures. The interactions between the bending and the torsional coordinates are responsible for the displacements of the torsional overtone bands and several combination bands. The effect of these interactions on the potential parameters is analyzed. Second order perturbation theory is used as a help for the understanding of many spectroscopic parameters and to obtain anharmonic fundamentals for the 3N - 9 neglected modes as well as the rotational parameters. To evaluate the surface accuracy and to verify previous assignments, the calculated vibrational levels are compared with experimental data corresponding to the most abundant isotopologue. The surface has been empirically adjusted for understanding the origin of small divergences between ab initio calculations and experimental data. Our calculations confirm previous assignments and show the importance of including the COC bending degree of freedom for computing with a higher accuracy the excited torsional term values through the Fermi interaction. Besides, this work shows a possible lack of accuracy of some available experimental transition frequencies and proposes a new assignment for a transition line. As an example, the transition 100 → 120 has been computed at 445.93 cm(-1), which is consistent with the observed transition frequency in the Raman spectrum at 450.5 cm(-1).     

Benchmarking NMR indirect nuclear spin-spin coupling constants: SOPPA, SOPPA(CC2), and SOPPA(CCSD) versus CCSD

Accurate calculations of NMR indirect nuclear spin-spin coupling constants require especially optimized basis sets and correlated wave function methods such as CCSD or SOPPA(CCSD). Both methods scale as N(6), where N is the number of orbitals, which prevents routine applications to molecules with more than 10-15 nonhydrogen atoms. We have therefore developed a modification of the SOPPA(CCSD) method in which the CCSD singles and doubles amplitudes are replaced by CC2 singles and doubles amplitudes. This new method, called SOPPA(CC2), scales only as N(5), like the original SOPPA-method. The performance of the SOPPA(CC2) method for the calculation of indirect nuclear spin-spin coupling constants is compared to SOPPA and SOPPA(CCSD) employing a set of benchmark molecules. We also investigate the basis set dependence by employing three different basis sets optimized for spin-spin coupling constants, namely the HuzIV-su4, ccJ-pVTZ, and ccJ-pVQZ basis sets. The results of the corresponding CCSD calculations are used as a theoretical reference.     

On the physisorption of water on graphene: a CCSD(T) study

The electronic structure of the zero-gap two-dimensional graphene has a charge neutrality point exactly at the Fermi level that limits the practical application of this material. There are several ways to modify the Fermi-level-region of graphene, e.g. adsorption of graphene on different substrates or different molecules on its surface. In all cases the so-called dispersion or van der Waals interactions can play a crucial role in the mechanism, which describes the modification of electronic structure of graphene. The adsorption of water on graphene is not very accurately reproduced in the standard density functional theory (DFT) calculations and highly-accurate quantum-chemical treatments are required. A possibility to apply wavefunction-based methods to extended systems is the use of local correlation schemes. The adsorption energies obtained in the present work by means of CCSD(T) are much higher in magnitude than the values calculated with standard DFT functional although they agree that physisorption is observed. The obtained results are compared with the values available in the literature for binding of water on the graphene-like substrates.     

On geometries of stacked and H-bonded nucleic acid base pairs determined at various DFT, MP2, and CCSD(T) levels up to the CCSD(T)/complete basis set limit level

The geometries and interaction energies of stacked and hydrogen-bonded uracil dimers and a stacked adeninecdots, three dots, centeredthymine pair were studied by means of high-level quantum chemical calculations. Specifically, standard as well as counterpoise-corrected optimizations were performed at second-order Moller-Plesset (MP2) and coupled cluster level of theory with single, double, and perturbative triple excitations [CCSD(T)] levels with various basis sets up to the complete basis set limit. The results can be summarized as follows: (i) standard geometry optimization with small basis set (e.g., 6-31G(*)) provides fairly reasonable intermolecular separation; (ii) geometry optimization with extended basis sets at the MP2 level underestimates the intermolecular distances compared to the reference CCSD(T) results, whereas the MP2/cc-pVTZ counterpoise-corrected optimization agrees well with the reference geometries and, therefore, is recommended as a next step for improving MP2/cc-pVTZ geometries; (iii) the stabilization energy of stacked nucleic acids base pairs depends considerably on the method used for geometry optimization, so the use of reliable geometries, such as counterpoise-corrected MP2/cc-pVTZ ones, is recommended; (iv) the density functional theory methods fail completely in locating the energy minima for stacked structures and when the geometries from MP2 calculations are used, the resulting stabilization energies are strongly underestimated; (v) the self-consistent charges-density functional tight binding method, with inclusion of the empirical dispersion energy, accurately reproduces interaction energies and geometries of dispersion-bonded (stacked) complexes; this method can thus be recommended for prescanning the potential energy surfaces of van der Waals complexes.     

Geometries, electronic structures, and excited states of UN2, NUO+, and UO 2 2+ : a combined CCSD(T), RAS/CASPT2 and TDDFT study

The ground- and excited-state geometries and electronic structures of the isoelectronic series of molecules UN₂, NUO⁺, and UO ₂ ²⁺ are investigated by using relativistic density functional theory (DFT) and ab initio wavefunction theory (WFT). Scalar relativistic and spin?Corbit-coupled quantum chemical methods at the CASPT2, RASPT2, CCSD(T), DFT and TDDFT levels are applied. Relativistic effects as elucidated by Pekka Pyykk? play an important role in these uranium compounds, in particular for the excited states. The three molecular species exhibit significantly different spectroscopic properties, concerning their excitation energies, bond lengths and vibrations. Density functional approaches yield qualitatively correct results for the ground states and the valence????U.7s,6d excited states. However, the performance of TDDFT for valence????U.5f type excitations (in particular of UN₂ and NUO⁺) is less satisfactory, indicating the importance of the self-interaction correction for such excitations.     

CCSD(T) expectation value calculations of first-order properties

An expectation value approach to calculations of first-order properties using the non-iterative, triple-excitation amplitudes in the coupled cluster wave function is exploited. Three methods are suggested and analysed using the many body perturbation theory (MBPT) expansion arguments. The first method, in which non-iterative triple-excitation amplitudes are used in the expression for the expectation values, makes the wave function accurate through the second order of MBPT. In the second method, which is an extension of the first, effects of triple-excitation amplitudes are coupled with single- and double-excitation amplitudes. The correlated density matrix equivalent through the fourth order to that obtained when CCSDT-la amplitudes are used is employed in the third method. The suggested methods are tested on dipole moment and polarizability calculations for several diatomic closed-shell molecules and are compared to other related approaches. Received: 15 May 1997 / Accepted: 5 June 1997     

A simple and efficient CCSD(T)-F12 approximation

A new explicitly correlated CCSD(T)-F12 approximation is presented and tested for 23 molecules and 15 chemical reactions. The F12 correction strongly improves the basis set convergence of correlation and reaction energies. Errors of the Hartree-Fock contributions are effectively removed by including MP2 single excitations into the auxiliary basis set. Using aug-cc-pVTZ basis sets the CCSD(T)-F12 calculations are more accurate and two orders of magnitude faster than standard CCSD(T)/aug-cc-pV5Z calculations.     

H-Atom abstraction from CH(3)NHNH(2) by NO(2): CCSD(T)/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) and CCSD(T)/6-311+G(2df,p)//CCSD/6-31+G(d,p) calculations

Stationary points of paths for H atom abstraction from CH(3)NHNH(2) (monomethylhydrazine) by NO(2) were characterized via CCSD(T)/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) and CCSD(T)/6-311+G(2df,p)//CCSD/6-31+G(d,p) calculations. Five transition states connecting CH(3)NHNH(2)-NO(2) complexes to a manifold that includes CH(3)NHNH-HONO, CH(3)NNH(2)-HONO, CH(3)NNH(2)-HNO(2), and CH(3)NHNH-HNO(2) complexes were identified. Transition states that connect CH(3)NHNH-HONO, CH(3)NNH(2)-HONO, CH(3)NNH(2)-HNO(2), and CH(3)NHNH-HNO(2) complexes to each other via H atom exchange and/or hindered internal rotation were also identified. The high point in the minimum energy path from the CH(3)NHNH(2) + NO(2) reactant asymptote to the manifold of HONO-containing product states is a transition state 8.6 kcal/mol above the reactant asymptote. From a kinetics standpoint, this value is considerably higher than the 5.9 kcal/mol value that was estimated for it based on theoretical results for H atom abstraction from NH(3) by NO(2).     

Implementation of the CCSD(T)-F12 method using cusp conditions

The explicitly-correlated coupled-cluster singles and doubles with perturbative triples method (CCSD(T)-F12) is implemented using the cusp conditions. Numerical tests for a set of 16 molecules have shown agreement of correlation energies within 1 mE(h) between the cusp-condition and fully-optimized CCSD(T)-F12 methods. Benchmark calculations on 13 chemical reactions with the cusp-condition CCSD(T)-F12 method reproduce experimental enthalpies within 2 kJ mol(-1). It is also shown that regular unitary-invariant ansatz cannot exactly satisfy singlet and triplet cusp conditions in open-shell situations. We present an extended ansatz which can handle both conditions exactly.     

Toward true DNA base-stacking energies: MP2, CCSD(T), and complete basis set calculations

Stacking energies in low-energy geometries of pyrimidine, uracil, cytosine, and guanine homodimers were determined by the MP2 and CCSD(T) calculations utilizing a wide range of split-valence, correlation-consistent, and bond-functions basis sets. Complete basis set MP2 (CBS MP2) stacking energies extrapolated using aug-cc-pVXZ (X = D, T, and for pyrimidine dimer Q) basis sets equal to -5.3, -12.3, and -11.2 kcal/mol for the first three dimers, respectively. Higher-order correlation corrections estimated as the difference between MP2 and CCSD(T) stacking energies amount to 2.0, 0.7, and 0.9 kcal/mol and lead to final estimates of the genuine stacking energies for the three dimers of -3.4, -11.6, and -10.4 kcal/mol. The CBS MP2 stacking-energy estimate for guanine dimer (-14.8 kcal/mol) was based on the 6-31G(0.25) and aug-cc-pVDZ calculations. This simplified extrapolation can be routinely used with a meaningful accuracy around 1 kcal/mol for large aromatic stacking clusters. The final estimate of the guanine stacking energy after the CCSD(T) correction amounts to -12.9 kcal/mol. The MP2/6-31G(0.25) method previously used as the standard level to calculate aromatic stacking in hundreds of geometries of nucleobase dimers systematically underestimates the base stacking by ca. 1.0-2.5 kcal/mol per stacked dimer, covering 75-90% of the intermolecular correlation stabilization. We suggest that this correction is to be considered in calibration of force fields and other cheaper computational methods. The quality of the MP2/6-31G(0.25) predictions is nevertheless considerably better than suggested on the basis of monomer polarizability calculations. Fast and very accurate estimates of the MP2 aromatic stacking energies can be achieved using the RI-MP2 method. The CBS MP2 calculations and the CCSD(T) correction, when taken together, bring only marginal changes to the relative stability of H-bonded and stacked base pairs, with a slight shift of ca. 1 kcal/mol in favor of H-bonding. We suggest that the present values are very close to ultimate predictions of the strength of aromatic base stacking of DNA and RNA bases.     

Ergosterol (provitamin D2) triplet state: an efficient sensitiser of singlet oxygen, O2(1 delta g), formation

The triplet state of ergosterol (provitamin D2) has been produced in benzene by pulse radiolysis and characterised in terms of absorption spectrum, lifetime, self-quenching properties and relaxed triplet energy. The amount of singlet oxygen, O₂(¹Δ_g), produced as a consequence of the oxygen quenching of this species has been determined by kinetic infrared emission spectroscopy. Ergosterol is significantly more efficient as a singlet oxygen sensitiser in benzene than is naphthalene, the absolute standard employed in this work.     

CCSDT and CCSD(T) calculations on model H-bonded and stacked complexes

The CCSD(T) and CCSDT interaction energies were determined for model planar H-bonded complexes (formamide…formamide, formamidine…formamidine) and stacked complexes (ethylene…ethylene, formaldehyde…formaldehyde). Various basis sets from the 6-31G*(0.25) to aug-cc-pVDZ were used. Difference between CCSD(T) and CCSDT interaction energies were small and become negligible (bellow 0.1 kcal/mol) if the aug-cc-pVDZ (or aug-cc-pVDZ/cc-pVDZ) basis set was applied. This result strongly supports the use of the CCSD(T) method for determination of true stabilization energies of extended complexes.